The present invention relates to a hair dye composition containing an aniline compound. In particular, the present invention relates to an oxidation hair dye composition which exhibits excellent spreadability, applicability, level-dyeing property and shampoo resistance. The present invention also relates to a method of dyeing hair with the hair dye composition.
Hair dyes are classified into groups of temporary hair colorants, semipermanent hair dyes and permanent hair dyes. The oxidation hair dyes are the most widely used among the permanent hair dyes. When a hair dye of this kind is applied to hair, the oxidative polymerization occurs to develop a color after the oxidation dye in the hair dye composition penetrates into hair and, as a result, the hair is chemically dyed. Therefore, the hair dye of this kind has a strong dyeing power and the color lasts for a long time. The oxidation hair dyes are usually of two-pack type to be used by mixing a first pack containing an oxidation dye with a second pack containing an oxidizing agent at the time of use and applying the obtained mixture to hair. However, the oxidation hair dyes of one-pack type which is in the form of a powder to be mixed with water at the time of the use, and three- or more-pack type are available. In any case, the oxidation hair dyes chemically dye hair by the oxidative polymerization reaction. Therefore, when the applicability of the oxidation hair dye to hair is insufficient, dyeing specks are easily formed. To prevent the formation of the dyeing specks, various ideas were proposed hitherto. For example, a solvent, a dispersion medium or the like is incorporated into the oxidation hair dye composition to improve the fluidity thereof so that the hair dye can be rapidly and uniformly applied to hair; or an improved thickening agent is used as described in Japanese Patent Unexamined Published Application (hereinafter referred to as xe2x80x9cJ. P. KOKAIxe2x80x9d) No. Hei 9-20628. However, a further improvement is demanded. In particular, a further improvement in the fastness is demanded so that the dyed hair is not decolored even after repeating the shampoo many times.
Therefore, an object of the present invention is to provide an oxidation hair dye composition excellent in spreadability, applicability, level-dyeing property and shampoo resistance.
Another object of the invention is to provide a method of dyeing hair with the oxidation hair dye composition.
The present invention provides a hair dye composition containing at least one of the compounds of the following general formulae (I) to (V): 
In formula (I), R1 represents an alkyl group, aryl group or heterocyclic group, R2 represents a substituent and Z represents an ethylene group or trimethylene group. When R1 is an alkyl or aryl group, at least one of R1 and Z is substituted by a substituent containing at least one of nitrogen atom, oxygen atom and sulfur atom. n represents 0 or an integer of 1 to 3. When n is 2 or higher, R2""s may be the same or different or they may form a ring. A represents an acid radical or, in other words, A-H is an acid, and m represents 0 or a positive integer.
In formula (II), R11 represents a substituent, and Y represents a tetramethylene, pentamethylene or hexamethylene group substituted by a substituent containing at least one of nitrogen atom, oxygen atom and sulfur atom. n1 represents 0 or an integer of 1 to 4. When n1 is 2 or higher, R11""s may be the same or different or they may form a ring. A part of Y and R11 do not form a ring together. A1 represents an acid radical or, in other words, A1-H is an acid, and m1 represents 0 or a positive integer.
In formula (III), R21 represents an alkyl, aryl or heterocyclic group, R23 represents a hydrogen atom or an alkyl, aryl or heterocyclic group, and RZ3 represents a substituent. nZ1 represents an integer of 2 to 8, and nZ2 represents 0 or an integer of 1 to 4. When nZ2 is 2 or higher, R23""s may be the same or different or together form a ring. R21 do not form a ring with R23 and do not have four or more hydroxyl groups in the molecule. A2 represents an acid radical or, in other words, A2-H is an acid, and m2 represents 0 or a positive integer.
In formula (IV), R41 represents a substituent and n41 represents 0 or an integer of 1 to 4. When n41 is 2 or higher, R41""s may be the same or different or together form a ring. A41 represents an acid radical or, in other words, A41-H is an acid, and m41 represents 0 or a positive integer.
In formula (V), R51 represents a hydrogen atom or an alkyl, aryl or heterocyclic group, R52 represents a substituent. n51 represents an integer of 1 to 4. When n51 is 2 or higher, R52s may be the same or different or together form a ring. R51 does not form a ring with R52. A51 represents an acid radical or, in other words, A51 -H is an acid, and m51 represents 0 or a positive integer.
The detailed description will be made on the compounds of the general formulae (I) to (V).
The term xe2x80x9calkyl groupsxe2x80x9d herein indicates linear, branched and cyclic alkyl groups which may have a substituent.
In general formula (I), R1 represents an alkyl group, aryl group or heterocyclic group. These substituents may be further substituted by other substituents such as those comprising, for example, halogen, oxygen, nitrogen, sulfur and/or carbon atom (e.g. alkyl, alkenyl, alkynyl, aryl, hydroxyl, nitro and cyano groups). When R1 is an alkyl group, it is preferred that among the carbon atoms in R1, elements other than hydrogen element and carbon element are bonded to the carbon atom directly bonded to the nitrogen atom in the general formula (I). When R1 is a heterocyclic group, the nitrogen atom bonded to R1 in the general formula (1) is preferably bonded to a carbon atom constituting the heterocyclic ring of the heterocyclic group. The alkyl groups are linear, branched or cyclic alkyl groups having 1 to 25 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, hydroxymethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2,3,4-trihydroxybutyl, 2,3,4,5-tetrahydroxypentyl, 2,3,4,5,6-pentahydroxyhexyl, methanesulfonamidomethyl, n-hexyl, n-decyl, n-octadecyl, 2-ethylhexyl, 2-hydoxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, carbamoylaminomethyl, 4-nitrobutyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethyl, 2-[2-(2-2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethyl, 2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxyethoxy) ethoxy]ethoxy)ethyl, 2-[2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethoxy]ethyl, 2-(2-[2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethoxy] ethoxy)ethyl, 2-(2-methoxyethoxy)ethyl, 2-[2-(2-methoxyethoxy)ethoxy] ethyl, 2-(2-[2-(2-methoxyethoxy)ethoxy]ethoxy)ethyl, 2-[2-(2-[2-(2-methoxyethoxy)ethoxy]ethoxy)ethoxy]ethyl, 2-(2-ethoxyethoxy)ethyl and 2-[2-(2-butoxyethoxy)ethoxy]ethyl groups.
The aryl groups are preferably those having 6 to 24 carbon atoms such as phenyl, naphthyl and p-methoxyphenyl groups. The heterocyclic groups are five-membered or six-membered, saturated or unsaturated heterocyclic groups containing 1 to 5 carbon atoms and at least one of oxygen, nitrogen and sulfur atoms. The number of the hetero atoms or elements constituting the ring may be one or more. The heterocyclic groups include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl and pyrazolyl groups.
R1 is preferably an alkyl group or an aryl group, particularly the alkyl group.
Preferred examples of R1 include methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2,3,4-trihydroxybutyl, 2,3,4,5-tetrahydroxypentyl, 2,3,4,5,6-pentahydroxyhexyl, n-hexyl, n-octyl, n-decyl, n-octadecyl, 2-ethylhexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy] ethoxy)ethyl, 2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethyl, 2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethyl, 2-[2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethoxy]ethyl, 2-(2-[2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy] ethoxy)ethoxy]ethoxy)ethyl, 2-(2-methoxyethoxy)ethyl, 2-[2-(2-methoxyethoxy)ethoxy]ethyl, 2-[2-(2-butoxyethoxy)ethoxy]ethyl, mercaptoethyl, pyrimidinyl, carboxymethyl, 2-carbamoylaminoethyl, sulfoethyl, 2-bromoethyl, phenyl and p-methoxyphenyl. Particularly preferred examples of R1 include methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2,3,4-trihydroxybutyl, 2,3,4,5-tetrahydroxypentyl, 2,3,4,5,6-pentahydroxyhexyl, n-hexyl, n-octyl, n-decyl, n-octadecyl, 2-ethylhexyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxylethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy] ethoxy)ethyl, 2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethyl, 2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethyl, 2-(2-[2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethoxy] ethoxy)ethyl, 2-(2-methoxyethoxy)ethyl, 2-[2-(2-methoxyethoxy)ethoxy] ethyl, 2-[2-(2-butoxyethoxy)ethoxy]ethyl, mercaptoethyl, pyrimidinyl, carboxymethyl, 2-carbamoylaminoethyl, sulfoethyl, 2-bromoethyl and phenyl.
More particularly preferred examples of R1 include methyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl, 3,4-dihydroxybutyl, 2,3,4,5,6-pentahydroxyhexyl, n-hexyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethyl, 2-[2-(2-[2-(2-hydroxyethoxy) ethoxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-15 [2-(2-hydroxyethoxy)ethoxy] ethoxy)ethoxy]ethoxy)ethyl, 2-(2-[2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethyl, 2-[2-(2-methoxyethoxy)ethoxy]ethyl, 2-[2-(2-butoxyethoxy)ethoxy]ethyl, mercaptoethyl, pyrimidinyl, carboxymethyl, 2-carbamoylaminoethyl, sulfoethyl and 2-bromoethyl. Further particularly preferred examples of R1 include methyl, 2-hydroxyethyl, 3-hydroxypropyl, 3,4-dihydroxybutyl, 2,3,4,5,6-pentahydroxyhexyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy] ethoxy)ethyl, 2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy] ethoxy)ethyl, and mercaptoethyl.
R2 represents a substituent. Examples of the substituents include halogen atoms and groups such as alkyl, aryl, heterocyclic, cyano, nitro, hydroxyl, carboxyl, sulfo, alkoxyl, aryloxy, acylamino, amino, alkylamino, anilino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyl, silyloxy, aryloxycarbonylamino, imido, heterocyclic thio, sulfinyl, phosphonyl, aryloxycarbonyl, acyl and mercapto groups. They may be substituted by an alkyl group, alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom, mercapto group or another substituent comprising oxygen atom, nitrogen atom, sulfur atom and/or carbon atom.
As for the detailed examples of substituents R2, the halogen atoms are, for example, fluorine atom and chlorine atom. The alkyl groups are linear, branched or cyclic alkyl groups having 1 to 25 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, hydroxymethyl, mercaptomethyl, 2-hydroxyethyl, 2-mercaptoethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, hydroxymethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxypropyl, 2,3-dimercaptopropyl, 3,4-dihydroxybutyl, methanesulfonamidomethyl, n-hexyl, 2-hydoxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, carbamoylaminomethyl, 4-nitrobutyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethyl, 2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethyl, 2-(2-methoxyethoxy)ethyl, 2-[2-(2-methoxyethoxy) ethoxy] ethyl, 2-(2-[2-(2-methoxyethoxy)ethoxy]ethoxy)ethyl, 2-[2.-(2-[2-(2-methoxyethoxy)ethoxy]ethoxy)ethoxy]ethyl, 2-(2-ethoxyethoxy)ethyl and 2-[2-(2-butoxyethoxy)ethoxy]ethyl groups.
The aryl groups are preferably those having 6 to 24 carbon atoms such as phenyl, naphthyl and p-methoxyphenyl groups. The heterocyclic groups are five-membered or six-membered, saturated or unsaturated heterocyclic groups containing 1 to 5 carbon atoms and at least one of oxygen, nitrogen and sulfur atoms. The number of the hetero atoms and the variety of the elements constituting the ring may be one or more. The heterocyclic groups include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl and pyrazolyl groups.
The alkoxyl groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxyl, ethoxyl, 2-mercaptoethoxyl, 2-methoxyethoxyl and 2-methanesulfonylethoxyl groups. The aryloxy groups are those having 6 to 24 carbon atoms such as phenoxy, p-methoxyphenoxy and m-(3-hydroxypropionamido)phenoxy groups. The acylamino groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetamido, 2-methoxypropionamido and p-nitrobenzoylamido groups.
The alkylamino groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as dimethylamino, diethylamino, bis(2-mercaptoethyl)amino and 2-hydroxyethylamino groups. The anilino groups are those having 6 to 24 carbon atoms such as anilino, m-nitroanilino and N-methylanilino groups. The ureido groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as ureido, methylureido, N,N-diethylureido and 2-methanesulfonamidoethylureido groups.
The sulfamoylamino groups are those having 0 to 16 carbon atoms, preferably 0 to 6 carbon atoms, such as dimethylsulfamoylamino, methylsulfamoylamino and 2-methoxyethylsulfamoylamino groups. The alkylthio groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methylthio, ethylthio and 2-phenoxyethylthio groups. The arylthio groups are those having 6 to 24 carbon atoms such as phenylthio, 2-carboxyphenylthio and 4-cyanophenylthio groups. The alkoxycarbonylamino groups are those having 2 to 16 carbon atoms, preferably 2 to 6 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino and 3-methanesulfonylpropoxycarbonylamino groups.
The sulfonamido groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonamido, p-toluenesulfonamido and 2-methoxyethanesulfonamido groups. The carbamoyl groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as carbamoyl, N,N-dimethylcarbamoyl and N-ethylcarbamoyl groups. The sulfamoyl groups are those having 0 to 16 carbon atoms, preferably 0 to 6 carbon atoms, such as sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl groups.
The sulfonyl groups are aliphatic or aromatic sulfonyl groups having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl, ethanesulfonyl and 2-chloroethanesulfonyl groups. The alkoxycarbonyl groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl groups. The heterocyclic oxy groups are five-membered or six-membered, saturated or unsaturated heterocyclic oxy groups containing 1 to 5 carbon atoms and at least one of oxygen, nitrogen and sulfur atoms. The number of the hetero atom(s) constituting the ring may be one or more, and when the ring contains two or more elements of the hetero atoms, the kind of them may be the same or different. Examples of the heterocyclic oxy groups include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy and 2-pyridyloxy groups.
The azo groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as phenylazo, 2-hydroxy-4-propanoylphenylazo and 4-sulfophenylazo groups. The acyloxy groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetoxy, benzoyloxy and 4-hydroxybutanoyloxy groups. The carbamoyloxy groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as N,N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxy groups.
The silyl groups are those having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyl, isopropyldiethylsilyl and t-butyldimethylsilyl groups. The silyloxy groups are those having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy groups. The aryloxycarbonylamino groups are those having 7 to 24 carbon atoms such as phenoxycarbonylamino, 4-cyanophenoxycarbonylamino and 2, 6-dimethoxyphenoxycarbonylamino groups.
The imido groups are those having 4 to 16 carbon atoms such as N-succinimido and N-phthalimido groups. The heterocyclic thio groups are five-membered or six-membered, saturated or unsaturated heterocyclic thio groups containing 1 to 5 carbon atoms and at least one of oxygen, nitrogen and sulfur atoms. The number of the hetero atom(s) constituting the ring may be one or more, and when the ring contains two or more elements of the hetero atoms, the kind of them may be the same or different. Examples of the heterocyclic thio groups include 2-benzothiazolylthio and 2-pyridylthio groups.
The sulfinyl groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfinyl, benzenesulfinyl and ethanesulfinyl groups. The phosphonyl groups are those having 2 to 16 carbon atoms, preferably 2 to 6 carbon atoms, such as methoxyphosphonyl, ethoxyphosphonyl and phenoxyphosphonyl groups. The aryloxycarbonyl groups are those having 7 to 24 carbon atoms such as phenoxycarbonyl, 2-methylphenoxycarbonyl and 4-acetamidophenoxycarbonyl groups. The acyl groups are those having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetyl, benzoyl and 4-chlorobenzoyl groups.
R2 is preferably a halogen atom, or an alkyl, heterocyclic, nitro, hydroxyl, carboxyl, sulfo, alkoxyl, acyloxy, amino, alkylamino, ureido, sulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, imido, heterocyclic thio, sulfinyl, phosphonyl, acyl or mercapto group. R2 is particularly preferably a halogen atom, or an alkyl, heterocyclic, hydroxyl, alkoxyl, alkylamino, ureido, sulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, heterocyclic oxy, heterocyclic thio or mercapto group. Among them, R2 is particularly preferably an alkyl, heterocyclic, alkoxyl, alkylamino, ureido, alkylthio or mercapto group.
Preferred examples of R2 include methyl, i-propyl, 2-mercaptoethyl, 2-thienyl, pyrazolyl, methoxy, isopropoxy, dimethylamino, ureido, methylthio, chlorine, 2,3-dihydroxypropyl and mercapto groups, or two R2""s may together form a furan ring.
More preferred examples of R2 include methyl, i-propyl, methoxy, chlorine, and 2,3-dihydroxypropyl, or two R2""s may together form a furan ring. Further preferred examples of R2 include methyl, i-propyl and methoxy.
Z represents ethylene group or trimethylene group having 2 to 30 carbon atoms, preferably 2 to 15 carbon atoms and more preferably 2 to 6 carbon atoms. The substituents of ethylene group or trimethylene group as Z are halogen atoms and substituents composed of nitrogen, oxygen, sulfur and/or carbon atoms (such as alkyl, alkenyl, alkynyl, aryl, hydroxyl, nitro and cyano groups). These substituents may be further substituted by other substituents. The substituents are those listed above with reference to R2. Preferred substituents include halogen atoms, and hydroxyl, alkyl, alkoxyl, carboxyl, acylamino, alkylamido, ureido, sulfamoylamino, alkoxycarbonylamino, sulfonylamino, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, acyloxy, carbamoyloxy, acyl and mercapto groups. Particularly preferred substituents are hydroxyl, alkyl, carboxyl, acylamino, ureido, alkoxycarbonylamino, sulfonylamino, carbamoyl, acyloxy, carbamoyloxy and mercapto groups. Still preferred substituents are hydroxyl, alkyl, carboxyl and mercapto groups. Examples of Z include ethylene, 1-methylethylene (the carbon bonded to the nitrogen atom is in the 1-position), 2-methylethylene, 1,2-dimethylethylene, 1,1,2-trimethylethylene, 1,2,2-trimethylethylene, 1,1,2,2-tetramethylethylene, 2-hydroxymethylethylene, 2-hydroxyethylene, 1-methyl-2-hydroxyethylene, 1,1,2-trimethyl-2-carboxyethylene, 1,1,2,2-tetraethylethylene, trimethylene, 1,1-dimethyltrimethylene, 2,2-dimethyltrimethylene, 3,3-dimethyltrimethylene, 1,1,3-trimethyltrimethylene, 1,1,3-trimethyl-2-decyltrimethylene, 1,1,3-trimethyl-2-methyltrimethylene, 1,1-diethyltrimethylene, 2,2-diethyltrimethylene, 3,3-diethyltrimethylene, 1,1,2,2,3,3-hexaethyltrimethylene 1,3-trimethyl-3-carboxytrimethylene, 1,1,3-trimethyl-2-hydroxytrimethylene 1,-dimethyl-2-hydroxy-3-methylidenetrimethylene, 1,1,3-trimethyl-2,3-dihydroxytrimethylene, 1,1,1,3-trimethyl-2-aminotrimethylene 1,1,-diyroxymethyl-32-dimethylaminotrimethylene, 1,3-trimethyl-2-bromotrimethylene, 1,1,3-trimethyl-2-(N-pyrazolyltrimethylene, 1,1-dihydroxymethyl-3-methyltrimethylene, 1,1-dimethyl-3-hydroxymethyltrimethylene, 1,1-dimethyl-3-formyltrimethylene, 1,1-dimethyl-3-carboxytrimethylene, 1,1-dimethyl-3-carbamoyltrimethylene 1,1-dimethyl-3-dimethylcarbamoyl trimethylene, 1,1-dimethyl-3-hydroxymethyl-2,3-dihydroxytrimethylene and 1, 1-dimethyl-3-hydroxymethyl-2-hydroxytrimethylene. Among them, particularly preferred examples include ethylene, 1-methylethylene, 2-methylethylene, 1,2-dimethylethylene, 1,2,2-trimethylethylene, 1,1,2,2-tetramethylethylene, 2-hydroxyethylene 1-methyl-2-hydroxyethylenetrimethylene, 1,1-dimethyltrimethylene, 2,2-dimethyltrimethylene, 3,3-dimethyltrimethylene, 1,1,3-trimethyltrimethylene, 1,1,3-triethyl-2-methyltrimethylene, 1,1,3-trimethyl-2-hydroxytrimethylene, 1,1,3-trimethyl-2,3-dihydroxytrimethylene, 1,1-dimethyl-3-hydroxymethyl trimethylene and 1,1-dimethyl-3-hydroxymethyl-2-hydroxytrimethylene. More preferred examples include ethylene, 1-methylethylene, 2-methylethylene, 1,2-dimethylethylenetrimethylene, 1,1-dimethyltrimethylene, 2,2-dimethyltrimethylene, 3,3-dimethyltrimethylene, 1,1,3-trimethyltrimethylene, 1,1,3-trimethyl-2-hydroxytrimethylene and 1,1-dimethyl-3-hydroxymethyltrimethylene.
A represents an acid radical. Namely, A-H represents an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, naphthalene-1,5-disulfonic acid, ascorbic acid or oxalic acid. A-H is preferably hydrochloric acid, sulfuric acid, p-toluenesulfonic acid or naphthalene-1,5-disulfonic acid. The most preferred A-H is sulfuric acid or naphthalene-1,5-disulfonic acid. m represents 0 or a positive integer. When m is 2 or above, two or more (A-H)""s may be the same or different.
In a preferred combination of R1, R2, Z and n, R1 is an alkyl group, R2 is an alkyl or alkoxyl group, Z is an ethylene or trimethylene group unsubstituted or substituted with a hydroxyl, alkyl or carboxyl group, which has 2 to 6 carbon atoms in total. n is 0 or 1.
Since R11 in the general formula (II) is the same as R2 in the general formula (I), R11 is the same as R2.
R11 is preferably a halogen atom, or an alkyl, heterocyclic, nitro, hydroxyl, carboxyl, sulfo, alkoxyl, acyloxy, amino, alkylamino, ureido, sulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, imido, heterocyclic thio, sulfinyl, phosphonyl, acyl or mercapto group. R11 is particularly preferably a halogen atom, or an alkyl, heterocyclic, hydroxyl, alkoxyl, alkylamino, ureido, sulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, heterocyclic oxy, heterocyclic thio or mercapto group. Among them, R11 is particularly preferably an alkyl, heterocyclic, alkoxyl, alkylamino, ureido, alkylthio or mercapto group.
Preferred examples of R11 include methyl, i-propyl, 2-mercaptoethyl, 2-thienyl, pyrazolyl, methoxy, isopropoxy, acetylamino, amino, dimethylamino, sulfamoylamino, carboxy, sulfo, phenyloxy, acetyl, dichlorophenylamino, carbamoylamino, sulfamoylamino, ureido, methylthio and mercapto groups, or two R11""s may together form a furan ring.
More preferred examples of R11 include methyl, isopropoxy, acetylamino, methoxy, i-propyl, amino, dimethylamino, sulfamoylamino, carboxy, sulfo, phenyloxy, acetyl, dichlorophenylamino, carbamoylamino, sulfamoylamino and methylthio, or two R11""s may together form a furan ring. Further preferred examples of R11 include methyl, isopropoxy, acetylamino, methoxy, i-propyl, amino, dimethylamino and sulfamoylamino.
Y represents tetramethylene, pentamethylene or hexamethylene group having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms and more preferably 4 to 8 carbon atoms, which is substituted by a substituent containing at least one of carbon, nitrogen, oxygen and sulfur atoms. Examples of the substituents include an alkyl, aryl, heterocyclic, cyano, nitro, hydroxyl, carboxyl, sulfo, alkoxyl, aryl oxy, acyloxy, amino, alkylamino, anilino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, imido, heterocyclic thio, sulfinyl, phosphonyl, aryloxycarbonyl, acyl and mercapto groups. They may be further substituted by an alkyl, alkenyl, alkynyl, aryl, hydroxyl, nitro, cyano or mercapto group or a halogen as well as another substituent comprising oxygen, nitrogen, sulfur and/or carbon atom. Examples of these substituents are the same as those described above with reference to R11.
Preferred substituents are hydroxyl, alkyl, alkoxyl, carboxyl, acylamino, alkylamino, ureido, sulfamoylamino, alkoxycarbonylamino, sulfonylamino, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, acyloxy, carbamoyloxy, acyl and mercapto groups. More preferred substituents are hydroxyl, alkyl, alkoxyl, carboxyl, acylamino, alkylamino, ureido, alkoxycarbonylamino, sulfonylamino, carbamoyl, acyloxy, carbamoyloxy and mercapto groups. Particulrly preferred substituents are hydroxyl, alkyl, carboxyl and mercapto groups.
Preferred Y are tetramethylene and pentamethylene groups. Tetrmethylene group is the most preferred.
In a preferred combination of the substituents R11, Y and Y with n1, R11 is an alkyl or alkoxyl group, Y is tetramethylene or pentamethylene group, the substituent of Y is a hydroxyl, alkyl, carboxyl or mercapto group, and n, is 0 or 1.
A1 represents an acid radical. Namely, A1-H represents an acid. Examples of A1-H are those described above with reference to A-H in formula (1). The most Preferred A1-H is sulfuric acid or naphthalene-1,5-disulfonic acid. m1 represents 0 or a positive integer. When m1 is 2 or above, two or more (A1-H)""s may be the same or different.
Since R21 in the general formula (III) is the same as R1 in the general formula (I), R21 is the same as R1.
R21 is preferably an alkyl or aryl group. It is most preferably an alkyl group.
Preferred examples of R21 include methyl, ethyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy] ethoxy)ethyl, 2-(2-[2-(2-[2-(2-(2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethyl, and 2-(2-methoxyethoxy)ethyl, hydroxybutyl, phenyl, benzyl, n-propyl, 2-(2-[2-(2-[2-(2-methoxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethyl, and 2-(2-phenoxyethoxy)ethyl. More preferred examples of R21 include methyl, ethyl, 2-(2-hydroxyethoxy)ethyl, 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, 2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethyl, 2-(2-[2-(2-[2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethoxy]ethoxy)ethyl, and 2-(2-methoxyethoxy)ethyl.
R22 represents a hydrogen atom or an alkyl, aryl or heterocyclic group. The alkyl, aryl and heterocyclic groups are the same as those listed above with reference to R21. Among them, the hydrogen atom, alkyl group such as methyl group and phenyl group are preferred. Hydrogen atom and methyl group are the most preferred. R23 represents a substituent. The substituents are those described above with reference to R11.
Preferred examples of R23 include trimethylsiloxy, phenoxycarbonyl, isopropoxy, i-propyl, methyl, mercaptoethyl, trimethylsilyl, succinimidyl, pyridylthio, sukfino, phenoxycarbonyl and methoxy. More preferred examples of R23 include trimethylsiloxy, phenoxycarbonyl, isopropoxy, i-propyl, methyl and mercaptoethyl.
n21 represents an integer of 2 to 8, preferably 2 to 6 and more preferably 2 to 4. R21 has particularly preferably a structure of the general formula: xe2x80x94(CH2CH2O)n23R24.
R24 in this formula represents a hydrogen atom or an alkyl, aryl or heterocyclic group. The alkyl, aryl and heterocyclic groups are the same as those described above with reference to R22. Among them, the hydrogen atom or alkyl group is preferred. The hydrogen atom is most preferred. n23 represents an integer of 2 to 8. The most preferably, R21 is a group of the general formula: xe2x80x94(CH2CH2O) n23R24 wherein n23 is the same as n21, and R24 is the same as R22.
Preferred compounds of the general formula (III) are those wherein R21 is represented by xe2x80x94(CH2CH2O)n23R24 wherein R24 is the same as R22 and represents a hydrogen atom or alkyl group, n23 is the same as n21 and represents an integer of 2 to 4, R23 represents an alkyl or alkoxyl group, and n22 is 0 or 1.
A2 represents an acid radical. Namely, A2-H represents an acid. Examples of A2-H are those described above with reference to A-H in formula (I). The most preferred A2-H is sulfuric acid or naphthalene-1,5-disulfonic acid. m2 represents 0 or a positive integer. When m2 is 2 or above, two or more (A2-H)""s may be the same or different.
Since R41 in the general formula (IV) is a substituent and is the same as R2 in the general formula (I), R41 is the same as R2.
R41 is preferably a halogen atom or an alkyl, heterocyclic, nitro, hydroxyl, carboxyl, sulfo, alkoxyl, acyloxyl, amino, alkylamino, ureido, ulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, imido, heterocyclic thio, sulfinyl, phosphonyl, acyl or mercapto group. R41 is particularly preferably a halogen atom, or an alkyl, heterocyclic, hydroxyl, alkoxyl, alkylamino, ureido, sulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, heterocyclic oxy, heterocyclic thio or mercapto group. Among them, R41 is particularly preferably an alkyl, heterocyclic, alkoxyl, alkylamino, ureido, alkylthio or mercapto group.
Preferred examples of R41 include methyl, ethyl, i-propyl, ethoxy, 2-mercaptoethyl, 2-thienyl, pyrazolyl, methoxy, isopropoxy, n-hexanoxy, dimethylpyrazolyl, dimethylamino, carbamoylamino, n-methyl-n-(dimethylaminocarbonyl) ureido, methylthio, ethylthio, mercapto, n-butylthio, n-octylthio, mercaptoethylthio and hydroxyethylthio groups.
More preferred examples of R41 include methyl, ethyl, i-propyl, ethoxy, isopropoxy, mercaptoethyl, methoxy, n-hexanoxy, dimethylpyrazolyl, dimethylamino, carbamoylamino, n-methyl-n-(dimethylaminocarbonyl) methylthio, ethylthio, mercapto, n-butylthio, n-octylthio, mercaptoethylthio and hydroxyethylthio. Further preferred examples of R41 include methyl, ethyl, i-propyl, ethoxy, isopropoxy and mercaptoethyl.
n41 represents an integer of 1 to 4, preferably 0 or 1.
A41 represents an acid radical. Namely, A41-H represents an acid. Examples of A41-H are those described above with reference to A-H in formula (I). The most preferred A41-H is sulfuric acid or naphthalene-1,5-disulfonic acid. m41 represents 0 or a positive integer. When m41 is 2 or above, two or more A41-H""s may be the same or different.
Since R51 in the general formula (V) represents a hydrogen atom or an alkyl, aryl or heterocyclic group, and is the same as R1 (but excepting the hydrogen atom) in the general formula (I), the same description given above for R1 is applied to R51.
R51 is preferably a hydrogen atom or an alkyl or aryl group. It is particularly preferably hydrogen or an alkyl group.
For preferred examples of R51 other than hydrogen atom, the same description given above for R1 is applied to R51.
Preferred examples of R51 include a hydrogen atom, methyl, n-hexyl, 2-(2-hydroxyethoxy)ethyl and phenyl. More preferred examples of R51 include a hydrogen atom, methyl and n-hexyl.
R52 is a substituent. The substituents R52 are the same as the substituents R41. The preferred substituents R52 include halogen atoms, and alkyl, heterocyclic, nitro, hydroxyl, carboxyl, sulfo, alkoxyl, acyloxyl, amino, alkylamino, ureido, ulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, imido, heterocyclic thio, sulfinyl, phophonyl, acyl or mercapto group. R52 is particularly preferably a halogen atom, or an alkyl, heterocyclic, hydroxyl, alkoxyl, alkylamino, ureido, sulfamoylamino, alkylthio, alkoxycarbonylamino, sulfonamido, heterocyclic oxy, heterocyclic thio or mercapto group. Among them, R52 is particularly preferably an alkyl, heterocyclic, alkoxyl, alkylamino, ureido, alkylthio or mercapto group.
Preferred examples of R52 include methyl, i-propyl, 2-mercaptoethyl, 2-thienyl, pyrazolyl, methoxy, isopropoxy, dimethylamino, ureido, methylthio and mercapto groups.
More preferred examples of R52 include methyl, ethyl, i-propyl, methoxy, ethoxy, isopropoxy, hydroxyethoxy, 1-methylheptyloxy, mercaptoethyl, methylthio, dimethylamino, mercapto and mercaptomethoxy, or two R52""s may together form a methylpyrrole ring. Further preferred examples of R52 include methyl, i-propyl, methoxy, methylthio, 1-methylheptyloxy, isopropoxy and hydroxyethoxy.
n51 represents an integer of 1 to 4, preferably 0 or 1.
A51 represents an acid radical. Namely, A51-H represents an acid. Examples of A51-H are those described above with reference to A-H in formula (I). The most preferred A51-H is sulfuric acid or naphthalene-1,5-disulfonic acid. m51 represents 0 or a positive integer. When m51 is 2 or above, two or more A51-H""s may be the same or different.
Examples of the compounds represented by the general formulae (I) to (V) of the present invention are given below, which by no means limit the invention. The stereostructures are not specified in the following formulae, and any possible stereostructure is possible. Mixtures of stereoisomers are also within the present invention. 
The relationship between these compounds and the general formulae (I) to (V) given above is as follows:
A-1 to A-55xe2x80x83xe2x80x83General formula (I) 
A2-1 to A2-25xe2x80x83xe2x80x83General formula (II) 
A2-26 to A2-45xe2x80x83xe2x80x83General formula (III) 
A4-1 to A4-20xe2x80x83xe2x80x83General formula (IV) 
A4-21 t A4-41xe2x80x83xe2x80x83General formula (V) 
4-Amino-N,N-dialkylaniline compounds represented by the general formula (I) of the present invention can be synthesized on the basis of, for example, Journal of the American Chemical Society, Vol. 73, p. 3100 (1951). They can be synthesized also according to the following synthesizing scheme 1 or processes based thereon. 
The compounds represented by the general formula (II) or (III) of the present invention can be synthesized by the following synthesizing scheme 2 or processes based thereon. The compounds represented by the general formula (IV) or (V) of the present invention can be synthesized according to the following synthesizing scheme 3 or processes based thereon. 
These compounds are synthesized by introducing an alkyl group, aryl group, heterocyclic group or the like into an amino group of an aniline forming a condensed ring with benzene. Namely, the starting compound is reacted with a halide, alkyl sulfonate, aryl sulfonate or the like. Then azo coupling at the p-position of the amino group is conducted, or a nitroso group or nitro group is introduced thereinto. The product is reduced (by the catalytic hydrogenation, reduction with zinc under acidic conditions, reduction with reducing iron or the like) and then converted into a salt with an acid to obtain the intended product.
The alkylation reaction is carried out by using one to five equivalents, preferably one to three equivalents, of a corresponding alkylating agent (per one equivalent of the alkylation) selected from among alkyl halides (alkyl chlorides, alkyl bromides and alkyl iodides) and alkyl sulfonates (such as alkyl mesylates and alkyl tosylates) and alkyl esters (such as alkyl acetates and alkyl benzoates)] in the presence of one to five equivalents (per one equivalent of the alkylation), preferably one to three equivalents, of an organic base (such as triethylamine or diazabicycloundecene) or an inorganic base (such as sodium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide); without using any solvent or in a solvent such as water, an amide solvent (such as N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone), a sulfone solvent (such as sulfolane), a sulfoxide solvent (such as dimethyl sulfoxide), an ureido solvent (such as tetramethylurea), an ether solvent (such as dioxane) or an alcohol solvent (such as isopropyl alcohol or butanol); in the absence or presence of a catalyst (such as sodium iodide); at a reaction temperature in the range of 0 to 200xc2x0 C., preferably 80 to 170xc2x0 C.; for a reaction time in the range of 10 minutes to 72 hours, preferably 30 minutes to 12 hours.
Then the azo coupling at the p-position to the amino group is conducted, or a nitroso group or nitro group is introduced thereinto. An embodiment of the azo coupling reaction is as follows: A substituted or unsubstituted aniline is converted into a diazonium salt thereof in the presence of an acid (organic or inorganic acid such as hydrochloric acid, sulfuric acid, methanesulfonic acid or acetic acid) without using any solvent or in water or an organic solvent (such as an alcohol solvent, e.g. methanol, ethanol or isopropyl alcohol; an amide solvent, e.g. N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone solvent, e.g. sulfolane; a sulfoxide solvent, e.g. dimethyl sulfoxide; or a ureido solvent, e.g. tetramethylurea) at a temperature in the range of xe2x88x9278 to 40xc2x0 C., preferably xe2x88x9220 to 30xc2x0 C. for a reaction time in the range of five minutes to five hours, preferably five minutes to one hour; and then one to five equivalents, preferably one to two equivalents, of the diazonium salt is coupled with an N,N-dialkylaniline without using any solvent or in water or an organic solvent (such as an alcohol solvent, e.g. methanol, ethanol or isopropyl alcohol; an amide solvent, e.g. N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone solvent, e.g. sulfolane, a sulfoxide solvent, e.g. dimethyl sulfoxide; or a ureido solvent, e.g. tetramethylurea) at a temperature in the range of xe2x88x9278 to 40xc2x0 C., preferably xe2x88x9220 to 30xc2x0 C. for a reaction time in the range of five minutes to five hours, preferably five minutes to one hour. The coupling reaction is preferably conducted under a weakly acidic to weakly basic condition. The nitrosation is conducted by, for example, using one to five equivalents, preferably one to two equivalents, of an organic nitrosating agent (such as isoamyl nitrite) or an inorganic nitrosating agent (such as sodium nitrite) in the presence of, for example, an acid (organic or inorganic acid such as hydrochloric acid, sulfuric acid, methanesulfonic acid or acetic acid) without using any solvent or in water or an organic solvent (such as an alcohol solvent, e.g. methanol, ethanol or isopropyl alcohol; an amide solvent, e.g. N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone solvent, e. g. sulfolane; a sulfoxide solvent, e.g. dimethyl sulfoxide; or a ureido solvent, e.g. tetramethylurea) at a temperature in the range of xe2x88x9278 to 40xc2x0 C., preferably xe2x88x9220 to 30xc2x0 C. for a reaction time in the range of five minutes to five hours, preferably five minutes to one hour. The nitration is conducted by, for example, using one to five equivalents, preferably one to 1.5 equivalents, of a varied concentration (60 to 98%) of nitric acid alone or in combination with an activator such as sulfuric acid, sulfuric anhydride, acetic anhydride or trifluoroacetic acid without using any solvent or in water or an organic solvent (such as an alcohol solvent, e.g. methanol, ethanol or isopropyl alcohol; an organic acid, e.g. acetic acid; an organic acid anhydride, e.g. acetic anhydride or trifluoroacetic anhydride; an amide solvent, e.g. N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone solvent, e.g. sulfolane; a sulfoxide solvent, e.g. dimethyl sulfoxide; or a ureido solvent, e.g. tetramethylurea) at a temperature in the range of xe2x88x9278 to 100xc2x0 C., preferably xe2x88x9220 to 30xc2x0 C., for a reaction time in the range of five minutes to five hours, preferably five minutes to one hour.
Finally, the product is reduced by the catalytic reduction with hydrogen, reduction with zinc under an acidic condition or reduction with reduced iron to obtain the intended product. The catalytic reduction pith hydrogen is conducted, for example, in the presence of a catalyst (such as palladium-carbon or Raney nickel) without using any solvent or in water or an organic solvent (such as an alcohol, e.g. methanol, ethanol or isopropyl alcohol; an amide, e.g. N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone, e.g. sulfolane; a sulfoxide, e.g. dimethyl sulfoxide, or a ureido, e.g. tetramethylurea) at a reaction temperature in the range of 0 to 150xc2x0 C., preferably 0 to 50xc2x0 C., under a hydrogen pressure in the range of 1 to 500 atm, preferably 1 to 200 atm. for a reaction time in the range of 5 minutes to 72 hour s, preferably 1 to 8 hours. The reduction with reduced iron is conducted, for example, with 4 to 10 equivalents, preferably 4 to 6 equivalents, of reduced iron and 0.0001 to 1 equivalent, preferably 0.001 to 0.1 equivalent, of an acid (an inorganic acid such as hydrochloric acid or sulfuric acid; or an organic acid such as acetic acid or methanesulfonic acid) or an acid salt (such as ammonium chloride, sodium chloride or sodium sulfate) alone or in combination of two or more of them without using any solvent or in water or an organic solvent (such as an alcohol, e.g. methanol, ethanol or isopropyl alcohol; an amide, e.g. N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone, e.g. sulfolane; a sulfoxide, e.g. dimethyl sulfoxide; or a ureido, e.g. tetramethylurea) at a reaction temperature in the range of 0 to 150xc2x0 C., preferably 50 to 100xc2x0xc2x0 C., for a reaction time in the range of 30 minutes to 72 hours, preferably 1 to 8 hours. The reduction with zinc under an acidic condition is conducted by using 3 to 10 equivalents, preferably 3 to 6 equivalents, of zinc powder in the presence of an acid (an organic acid such as acetic acid or methanesulfonic acid; or an inorganic acid such as hydrochloric acid or sulfuric acid) without using any solvent or in water or an organic solvent (such as an alcohol, e.g. methanol, ethanol or isopropyl alcohol, an organic acid, e.g. acetic acid; an amide, e.g. N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone, e.g. sulfolane; a sulfoxide, e.g. dimethyl sulfoxide; a ureido, e.g. tetramethylurea; or an organic acid such as acetic acid, propionic acid or methanesulfonic acid) at a reaction temperature in the range of 0 to 150xc2x0 C., preferably 0 to 100xc2x0 C., for a reaction time in the range of 5 minutes to 72 hours, preferably 30 minutes to 3 hours.
The products obtained by the above-described reactions are after-treated as in ordinary organic synthesis reactions and then purified if necessary. Namely, for example, the product isolated from the reaction system can be used without the purification or after the purification by the recrystallization, column chromatography or the like, or a combination of these techniques. It is also possible to use the product, after the completion of the reaction, by distilling off the reaction solvent if necessary, pouring the product into water or ice, neutralizing it if necessary, and purifying the isolated product by the recrystallization, column chromatography or the like or by a combination of these techniques, if necessary. Alternatively, it is also possible to use the product, after the completion of the reaction, by distilling off the reaction solvent if necessary, pouring the product into water or ice, neutralizing it if necessary, extracting the product with an organic solvent and purifying the extract, if necessary, by the crystallization or column chromatography or by the combination of these techniques.
Then the description will be given on examples of the synthesis of various anilines each forming a condensed ring with a benzene ring. 
The dihydroindole skeleton is obtained by the Fischer""s indole synthesis method from an arylhydrazine, followed by the reduction of the obtained indole compound or indolenine compound. 
Alternatively, a hydroxymethyl group is introduced in the benzyl position, the obtained product is chlorinated and then fused with the amino group at the 2-position of the benzene ring according to a method described in Journal of the Organic Chemistry, Vol. 55, P. 580 (1990). 
The tetrahydroquinoline skeleton can be dehydration-condensed with aniline and acetone and then the obtained product is reduced to obtain corresponding 2,2,4-trimethyltetrahydroquinoline according to a method described in Organic Synthesis Collective Volume, Vol. III, p. 328. 
It is also possible to use N-allylaniline and zinc (II) chloride to obtain a corresponding tetrahydroquinoline according to a method described in Nippon Kagaku Kaishi (Journal of Chemical Society Japan) P. 1043 (1981) as described above. 
Further, the tetrahydroquinoline skeleton can be obtained by the Friedel-Crafts reaction of an xcex1,xcex2-unsaturated amide and the reduction of the amide according to a method described in Journal of the Americann Chemical Society, Vol. 62, p. 778 (1940) as described above.
Thus, various substituents can be introduced into the propylene chain in the tetrahydroquinoline structure by using the intermediates constituting the basic skeleton. Examples of them are given below. 
The compounds of general formula (II) can be synthesized by, for example, using a dihalide or by introducing two alkyl groups and then closing a ring by a carbon-to-carbon bond-forming reaction. 
In the synthesis of the compounds of general formulae (II) to (V), the substitution reaction of a halobenzene compound with an amino compound can be employed as described above.
Further, as described above, the substitution reaction can be conducted by using a secondary amine compound having R1 and R2 or a primary amine compound having only R1.
The substitution reaction is carried out by using, for example, one equivalent of a fluorobenzene compound, chlorobenzene compound, bromobenzene compound or iodobenzene compound as the halobenzene compound and one to five equivalents, preferably one to three equivalents, of the amino compound in the absence of any base or in the presence of one to five equivalents, preferably one to three equivalents, of an organic base (such as triethylamine or diazabicycloundecene) or an inorganic base (such as sodium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide); without using any solvent or in a solvent such as water, an amide solvent (such as N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone), a sulfone solvent (such as sulfolane), a sulfoxide solvent (such as dimethyl sulfoxide), an ureido solvent (such as tetramethylurea), an ether solvent (such as diethyl ether, tetrahydrofuran or dioxane) or an alcohol solvent (such as methanol, ethanol, isopropyl alcohol, butanol or ethylene glycol) alone or in combination of two or more of them; in the absence or presence of a catalyst [such as copper (I) iodide, tetrakistriphenylphosphine palladium (0) or palladium chloride alone or in combination of two or more of them] at a reaction temperature in the range of 0 to 200xc2x0 C., preferably 25 to 180xc2x0 C.; for a reaction time in the range of 10 minutes to 72 hours, preferably 30 minutes to 12 hours. When a compound having a nitro group in the p-position to Y is used in this reaction, the first substitution reaction easily proceeds. This is effective for the synthesis of a compound of general formula (V) having a saccharide group at the N-position.
Examples for synthesizing the compounds of the present invention are given below.